Substituted-cyclopropyl sulfones

ABSTRACT

Novel 2-vinyl- and 2-ethyl-cyclopropyl sulfones are provided. In addition to the ethyl or vinyl group at the 2-position of the ring, the compounds of this invention are disubstituted at the 1-position with a sulfonyl group and an acyl, nitrile or nitrile-derived radical. The sulfones of this invention are useful chemical intermediates from which a wide variety of pesticidal, herbicidal or biologically active compounds can be prepared and are useful monomers for anionic or radical polymerizations.

This application is a division, of application Ser. No. 345,875, filedFeb. 4, 1982 now U.S. Pat. No. 4,446,077.

BACKGROUND OF THE INVENTION

1. Field of the Invention:

The present invention is directed to novel substituted-cyclopropylsulfones. More specifically, in addition to having a sulfonyl ##STR1##group on the ring, the compounds of this invention have a vinyl or ethylgroup substituted in the 2-position and an acyl moiety or nitrile orradical derived therefrom present with the sulfonyl group in the1-position. The sulfones of this invention are useful chemicalintermediates and undergo anionic or radical polymerizations.

2. Discussion of the Prior Art:

The polymerization of 1,1-disubstituted 2-vinylcyclopropanes has beendocumented by Iwhan Cho and co-workers (see Journal of Polymer Science,Vol. 17, 3169-3182(1979); Vol. 17, 3183-3191(1979); Vol. 18,3053-3057(1980); and Polymer Letters Edition, Vol. 18(9), 639-42(1980).In addition to radical initiated 1,5-type polymerizations, it was alsoobserved that anionic polymerization can be accomplished with suchcompounds via ring-opening and without participation of the vinyl group.It is thus possible to achieve reactive polymeric materials having avinyl group and nitrile or ester moiety pendant to the polymer chain.

In view of the desirable properties generally attributed to the presenceof sulfonyl groups in polymeric materials, it would be highly desirableand advantageous to have a reactive cyclopropyl monomer bearing suchsubstituents which could be readily polymerized under anionic or radicalconditions in accordance with the prior art teachings. However, thepreparation of such compounds has heretofore not been possible in viewof the limitations of the condensation procedures typically used toprepare cyclopropane derivatives. While E. V. Dehmlow report thepreparation of a cyclopropane compound having a sulfonyl groupsubstituted thereon via a carbene insertion reaction (Angew Chem.Internat. Edit., Vol. 13, No. 3, 170-179(1974), the reaction is notsuitable for the preparation of vinyl-substituted cyclopropane sulfones.

SUMMARY OF THE INVENTION

We have now quite unexpectedly discovered substituted-cyclopropylsulfones useful as chemical intermediates and reactive monomers. Thenovel substituted-cyclopropyl sulfones are prepared using thephase-transfer process of U.S. Pat. No. 4,252,739 and are disubstitutedat the 1-position of the ring and have a vinyl or ethyl group in the2-position.

The compounds of this invention correspond to the formula ##STR2## whereR represents an ethyl or vinyl group, R₁ represents a hydrocarbonradical of from 1 to 30 carbon atoms, and Y is an acyl radical, nitrileor nitrile-derived radical, such as an amine, quaternary amine, amide orcarboxylate. Preferably R₁ will be an aliphatic, cycloaliphatic oraromatic moiety having from 1 to 20 carbon atoms. Particularly preferredacyl moieties correspond to the formula ##STR3## where R₂ is ahydrocarbon radical as defined for R₁.

Especially useful cyclopropane compounds have the formulae ##STR4##wherein R₃ and R₅ are, independently, C₁₋₈ alkyl, C₃₋₈ alkenyl,cyclohexyl, phenyl, benzyl or C₁₋₄ alkyl-substituted cyclohexyl, phenylor benzyl and R₄ is hydrogen or a radical as defined for R₃ and R₅.

DETAILED DESCRIPTION

The novel substituted-cyclopropyl sulfones of this invention have thegeneral formula ##STR5## where R is an ethyl or vinyl group, R₁ is ahydrocarbon radical having from 1 to 30 carbon atoms, and Y is an acylgroup, nitrile or nitrile-derived radical. Whereas the formula does nottake into account the various isomeric forms of these compounds whichcan exist, i.e., geometric and stereo isomers and mixtures and racematesthereof, all such products are within the scope of this invention.

The hydrocarbon radical R₁ can contain from 1 up to 30 carbon atoms andmay be aliphatic, cycloaliphatic, aromatic or a combination of suchmoieties. When R₁ is an alkyl group, i.e., an aliphatic hydrocarbonradical, it will contain from 1 to 30 and, more preferably, 1 to 20carbon atoms and may be straight-chain or branched, saturated orunsaturated. Radicals which contain unsaturation generally have no morethan one double bond for every four carbon atoms.

Cycloaliphatic hydrocarbon radicals from which R₁ may be selected aresaturated or unsaturated and can contain one or more hydrocarbonsubstituents on the ring. The cycloaliphatic radicals will have from 3to 30 carbon atoms, however, preferred cycloaliphatic radicals containfrom 5 to 20 carbon atoms and correspond to the formula ##STR6## where mis an integer from 0 to 8 and, more preferably, 0 to 4, A represents anon-aromatic 5- or 6-membered carbon ring system, and R' and R" arehydrogen, a C₁₋₈ alkyl or alkenyl group, phenyl or benzyl. Particularlyadvantageous cycloaliphatic radicals of the above type are those whereinthe moiety ##STR7## is an unsubstituted or mono- C₁₋₈ alkyl- oralkenyl-substituted cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenylor cyclohexa-2,4-dienyl group.

When R₁ is an aromatic hydrocarbon radical, it will contain from 6 up toabout 30 carbon atoms and may consist of a single ring or fused-ringsystem which can be unsubstituted or have one or more hydrocarbon groupssubstituted thereon. Especially useful aromatic radicals contain from 6to 20 carbon atoms and correspond to the formula ##STR8## where m is aninteger from 0 to 8, and more preferably 0 to 4, and R' and R" arehydrogen, a C₁₋₈ alkyl or alkenyl group, phenyl or benzyl. Preferredaromatic radicals include phenyl, C₁₋₈ alkyl- or alkenyl-substitutedphenyl, benzyl and C₁₋₈ alkyl- or alkenyl-substituted benzyl.

When Y is an acyl group, R₂ is a hydrocarbon radical of 1 to 30 carbonatoms. R₂ can be selected from any of the groups defined above for R₁and can be the same as or different than R₁. Preferably, R₂ will be aC₁₋₈ alkyl, C₃₋₈ alkenyl, phenyl, benzyl or C₁₋₄ alkyl-substitutedphenyl or benzyl. More than one alkyl substituent may be present on thering and it is also possible to have C₁₋₄ alkoxyl groups substitutedthereon.

Y can also be nitrile --C.tbd.N) or any radical derived therefrom suchas amines, quaternary amines, amides or carboxylates. The hydrogenationof nitriles to produce amines is well known. Also, it is equally wellrecognized to hydrolyze nitriles to obtain the corresponding amideand/or carboxylic acid, depending on the conditions used and the degreeof hydrolysis. From the amine, amide and carboxylic acid groups, it ispossible to obtain a variety of other derivatives using establishedreaction procedures. For example, the carboxyl group can be reacted withalcohols, alkanolamines, poly(oxyalkylene)glycols, monoalkyl ethers ofpoly(oxyalkylene)glycols, and the like.

By judicious derivatization of the cyclopropyl sulfones in the abovemanner, it is possible to obtain useful 2-ethyl and 2-vinylcyclopropanecompounds having a sulfonyl group and an ester group substituted at the1-position of the ring and which exhibit biological activity, herbicidalproperties or pesticidal properties. Such compounds have the formula##STR9## where R and R₁ are the same as defined above and R"' is aheteroalkyl or heterocyclic group having from 3 to 20 carbon atoms.Particularly useful heteroalkyl and heterocyclic radicals include:##STR10## where R* is a C₁₋₄ alkyl, C₁₋₄ alkenyl, C₁₋₄ hydroxyalkyl,phenyl or benzl, Me is methyl, Et is ethyl, y is an integer from 2 to 6,z is an integer from 1 to 10 and X represents an anion such as halide,hydroxide, sulfate, nitrate, acetate, alkylsulfate, alkylphosphate,fluoroborate and the like.

Depending on the nature of the ester (R"') group, it is possible toobtain herbicidal compounds capable of modifying plant growth includingretardation of growth, defoliation, dessication, regulation,stimulation, dwarfing and, in some cases, killing the plant. In additionto products useful for the treatment of established plants and emergingseedlings, compounds useful as seed coatings are obtainable.Insecticidal compositions useful for the control of beetles, flies,mosquitos, spiders, lice, mites, ticks, nemotodes and other pests canalso be produced. Still other compounds which exhibit biologicalactivity can be obtained in this same manner.

To obtain such products, the cyclopropane carboxylic acid, acid halideor lower alkyl ester thereof, is typically utilized. Any process whichis non-destructive to the cyclopropane ring can be employed. Forexample, the cyclopropane carboxylic acid, can be directly reacted withthe desired alcohol or alcohol mixture employing conventionalesterification procedures and suitable conditions. Alkali salts of theaforementioned acids may also be reacted with suitable active halidecompounds to produce the desired cyclopropyl esters. Acid halides of thevinyl- or ethylcyclopropane can also be reacted with the alcohol orcorresponding alkali metal alkoxide. The carboxylates can also beobtained by transalcoholysis of a lower alkyl ester, preferably methylor ethyl, of the cyclopropane carboxylic acid with the desired alcoholor mixture of alcohols. Transalcoholysis of the cyclopropane lower alkylesters is carried out in accordance with conventional procedures.

By virtue of their reactivity and ability to be polymerized under eitheranionic or radical conditions, the 2-vinylcyclopropyl sulfones areparticularly advantageous. These compounds undergo both 1,2-typepolymerization via the vinyl group and 1,5-type polymerization through aring-opening mechanism. It is possible, utilizing the 2-vinylcyclopropylsulfones, to obtain polymeric materials having a sulfonyl group pendantto the polymer chain. While the vinylcyclopropyl sulfones can behomopolymerized, primarily the compounds of this invention are utilizedto modify the properties of known polymeric materials and arecopolymerized in minor amounts with one or more other monomers.Depending on the polymerization conditions, the comonomers, and theparticular 2-vinylcyclopropyl sulfone used, polymeric products havingwidely divergent physical properties can result. Especially useful2-vinylcyclopropyl sulfones for this purpose include: ##STR11## where R₃and R₅ are, independently, selected from C₁₋₈ alkyl, C₃₋₈ alkenyl,cyclohexyl, phenyl, benzyl or C₁₋₄ alkyl-substituted cyclohexyl, phenyland benzyl, and R₄ is hydrogen or a radical as defined for R₃ and R₅.

In addition to the sulfones, sulfoxides corresponding to the aboveformulae can be obtained in a similar manner following the process ofU.S. Pat. No. 4,252,739. Such compounds will have a sulfinyl ##STR12##group substituted at the 1-position on the ring. The remaining ringsubstituents can be the same as described above, i.e. an acyl, nitrileor nitrile-derived group in the 1-position and an ethyl or vinyl groupin the 2-position. The sulfinyl groups will be of the same general typeas defined for the sulfonyl moieties.

The following examples illustrate more fully the preparation of thenovel substituted-cyclopropyl sulfones of this invention. The examplesare not intended as a limitation on the scope of the invention. Numerousvariations are possible and will be evident to those skilled in the artto which the invention pertains.

EXAMPLE I

1-Phenylsulfonyl-1-cyano-2-vinylcyclopropane was obtained by the phasetransfer reaction of phenylsulfonylacetonitrile and 1,4-dichlorobutene-2in accordance with the procedure of U.S. Pat. No. 4,252,739. For thereaction 22.4 g (0.4 mol) potassium hydroxide and 4.04 gtricaprylylmethylammonium chloride were charged to a glass reactorequipped with a stirrer, thermometer and dropping funnel with 200 ccmethylene dichloride. To this mixture was added 36.2 g (0.2 mol)phenylsulfonylacetonitrile (Parish Chemical Co.) while gradually heatingto 28° C. with agitation. 1,4-Dichlorobutene-2 (27.5 g, 0.22 mol) wasthen added dropwise with the application of external cooling at a ratesuch that the temperature of the reaction mixture did not exceed 31° C.The reaction mixture was maintained with stirring at 28° C. for about 20hours, filtered and methylene chloride removed under vacuum. Theresulting viscous dark brown residue was extracted several times withhot isopropanol and hexane to yield a greenish-yellow solid. By repeatedrecrystallization of the solid from 95% ethanol/5% methanol, highly pure1-phenylsulfonyl-1-cyano-2-vinylcyclopropane ##STR13## was obtained aswhite crystals having a short needle-like structure (M.p. 80.0°-80.5°C.). Elemental analysis (C,H and N) of the product agreed with thecalculated theoretical values. The structure was also confirmed by massspectroscopy and nuclear magnetic resonance spectroscopy.

Mass spectrum m/e 233(M+) nmr (CDCl₃)τ 1.75-2.55(5 phenyl H, mult.);4.00-4.85 (3 vinyl H, mult.); 6.60-7.30 (1H(2 cyclopropyl ringposition), b. mult.); 7.65-8.40(2H(3 cyclopropyl ring position), welldefined mult.).

Similar results are obtained using methylsulfonylacetonitrile. Also,1-phenylsulfonyl-1-cyano-2-ethylcyclopropane is obtained by carrying outa reduction of the vinyl group using tosyl hydrazine. The reduction ofthe 1-phenylsulfonyl-1-cyano-2-vinylcyclopropane is accomplished in asuitable solvent medium, such as diglyme.

A polymeric material was produced when1-phenylsulfonyl-1-cyano-2-vinylcyclopropane was heated withα,α'-azobisisobutyronitrile or benzoyl peroxide at 95° C. Similarly,copolymers are obtained when1-phenylsulfonyl-1-cyano-2-vinylcyclopropane is combined withacrylonitrile and copolymerized.

EXAMPLE II

In a manner similar to that described in Example I,phenylsulfonylacetone was reacted with 1,4-dichlorobutene-2 to prepare1-phenylsulfonyl-1-acetyl-2-vinylcyclopropane. For the reaction, 9.91 g(0.05 mol) phenylsulfonylacetone (Parish Chemical Co.) and 6.25 g (0.05mol) 1,4-dichlorobutene-2 were combined in 20 cc sulfolane containing 5mole percent tricaprylylmethylammonium chloride and crushed 85%potassium hydroxide (6.6 g; 0.10 mol) added in small portions withstirring over a 10 minute period. The reaction mixture was then stirredat 35°-40° C. for about 31/2 hours. At the completion of the reaction,100 cc water was added to dissolve the white granular precipitate whichhad formed and the mixture extracted several times with ether. A crudered oil (10.8 g) was obtained after removal of the ether. Both the cisand trans isomers of 1-phenylsulfonyl-1-acetyl-2-vinylcyclopropane##STR14## were obtained upon further workup of the crude material andemploying a Waters Preparatory Liquid Chromatograph 500A equipped with agel permeation column and operated at a flow rate of 0.1 l/min. trans1-phenylsulfonyl-1-acetyl-2-vinylcyclopropane

mass spectrum m/e 250(M+) nmr (CDCl₃)τ 1.80-2.37(5 phenyl H, mult.);4.20-4.75 (3 vinyl H, mult.); 6.60-7.75(1H(2 cyclopropyl ring position),b mult.); 7.60(3H(CH₃ CO--),s.); 7.85-8.2(2H(3 cyclopropyl ringposition), mult.).

cis 1-phenylsulfonyl-1-acetyl-2-vinylcyclopropane

mass spectrum m/e 250(M+) nmr (CDCl₃)τ 1.80-2.45(5 phenyl H, mult.);3.45-5.05 (3 vinyl H, br. vinyl pattern); 7.60(1H(2 cyclopropyl ringposition), br. mult. centered at 7.50τ); 7.55(3H(CH₃ CO--), s.);8.00-9.15(2H(3 cyclopropyl ring position), well defined mult.).

When methylsulfonylacetone, α-methylsulfonylacetophenone,α-phenylsulfonylpinacolone, α-phenylsulfonylacetophenone andphenylsulfonylacetone are reacted with 1,4-dichlorobutene-2 or1,4-dibromobutene-2 in a similar manner, the corresponding cyclopropylsulfones and sulfoxide are obtained. All of these compounds polymerizeunder anionic or radical conditions.

We claim:
 1. A compound of the formula ##STR15## wherein R₃ and R₅ areC₁₋₈ alkyl, C₃₋₈ alkenyl, cyclohexyl, phenyl, benzyl or C₁₋₄alkyl-substituted cyclohexyl, phenyl or benzyl. 2.1-Phenylsulfonyl-1-acetyl-2-vinyl-cyclopropane.